A raw natural gas containing water, heavy hydrocarbons, acid compounds such as carbon dioxide (CO2) and hydrogen sulfide (H2S), and sulfur derivatives such as mercaptans, can be treated by means of the methods described by documents FR-2,605,241 and FR-2,636,857. These methods use a physical solvent such as methanol for dehydration, gasoline extraction and removal of the acid compounds and of the mercaptans. After this treatment, the gas meets the requirements as regards the CO2 content, typically below 2% by mole, and the H2S content, typically 4 ppm by mole.
Another gas treatment solution consists in carrying out deacidizing by means of a method using an amine solvent. Part of the light mercaptans, notably methylmercaptan, is removed during this stage. The heavier mercaptans, such as ethyl-, propyl- and butyl-mercaptan, are not sufficiently acid to significantly react with the amines and therefore remain in the gas in a large proportion.
The gas is then dehydrated by means of a method using a solvent such as glycol, for example the method described by document FR-2,740,468. Dehydration allows the water content of the gas to be lowered to a value close to 60 ppm by mole.
Besides, a TSA (Thermal Swing Adsorption) type adsorption method on a molecular sieve, for example of 3, 4A or 13X type, or on silica gel or alumina, can be used. In this case, the water content of the gas is typically below 1 ppm by mole.
The aforementioned methods allow to obtain a natural gas whose water, acid compound and heavy hydrocarbon contents in the natural gas treated meet the commercial requirements. However, the methyl- and ethyl-mercaptans still remain predominantly in the gas, in proportions that can reach 200 ppm or more in sulfur equivalent. For certain uses, these mercaptan proportions are too high.
One object of the present invention is to provide a natural gas purification method in order to obtain a mercaptan molar content below 10 ppm in sulfur equivalent.
It is possible to use a removal method using mercaptan adsorption. The conventional gas phase adsorption methods are the methods commonly referred to as TSA (Thermal Swing Adsorption) wherein the adsorption stage takes place at ambient or moderate temperature typically ranging between 200° C. and 350° C., in a purge gas sweep stream (in general part of the purified gas) whose flow rate ranges between 5% and 20% of the flow rate of the feed gas. The desorption gas containing a large amount of mercaptans then has to be treated prior to being recycled, for example by treatment with a basic solution (soda or potash), or it can be sent to the flare, which is neither economically nor ecologically advantageous. The pressure is either kept substantially constant throughout the cycle, or lowered during the regeneration stage so as to favour regeneration. After this stage of purification by adsorption, the water content of the gas is below 1 ppm by mole, and the gas meets the total sulfur requirements.
However, adsorption of the mercaptans by means of a conventional TSA method used in the industry, and notably to purify a natural gas, has several drawbacks. The following can be mentioned in particular:    long cycle times, in general rarely less than 4 hours, more often ranging between 8 and 12 hours, sometimes more, because of the thermal inertia of the adsorbent material,    immobilization of the adsorbent material because of the long cycle times, only the material transfer zone consisting of the adsorption fronts of the various compounds in the adsorber being really used, for adsorption as well as for regeneration,    necessity to heat to high temperatures, which leads to premature aging of the adsorbent material, notably during the desorption of thermally fragile products (under the effect of the thermal treatments regularly applied during the adsorbent material regeneration stage, the mercaptans can form reactive compounds and react with the co-adsorbed hydrocarbons so as to eventually lead to premature aging of the adsorbent material, which may require frequent renewal thereof, and thus an additional cost),    use of a large amount of purge gas, generally ranging between 5% and 20% of the flow rate of gas to be treated,    necessity to treat the purge gas containing the desorbed products and to recycle the purge gas.
The present invention provides a method of purifying a natural gas by mercaptan adsorption, avoiding the drawbacks of the methods from the prior art.